CN102357331A - Moisture absorbent composition, moisture absorbent molding, and method for controlling equilibrium humidity, method for controlling time of maintaining equilibrium humidity - Google Patents
Moisture absorbent composition, moisture absorbent molding, and method for controlling equilibrium humidity, method for controlling time of maintaining equilibrium humidity Download PDFInfo
- Publication number
- CN102357331A CN102357331A CN201110165375XA CN201110165375A CN102357331A CN 102357331 A CN102357331 A CN 102357331A CN 201110165375X A CN201110165375X A CN 201110165375XA CN 201110165375 A CN201110165375 A CN 201110165375A CN 102357331 A CN102357331 A CN 102357331A
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- CN
- China
- Prior art keywords
- thermoplastic resin
- hygroscopic agent
- moisture absorbent
- resin
- equilibrium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- C08J2323/08—Copolymers of ethene
Abstract
A moisture absorbent composition and a moisture absorbent molding respective contain a thermoplastic resin kneaded with a moisture absorbent. For preparing the composition and the molding, different equilibrium humidities can be obtained by changing the same kind resins with different specific gravities. An environment suitable for keeping various products can be simply formed. The moisture absorbent composition comprises the thermoplastic resin kneaded with the moisture absorbent having an equilibrium vapor pressure, the moisture absorbent is magnesium sulfate represented by the formula MgSO4.nH2O (0 <= n <= 3). A surface of the moisture absorbent is coated with a fatty acid metal salt so that the moisture absorbent comes to have a secondary particle size of substantially 1 to 40 [mu]m when dispersed in the thermoplastic resin. The equilibrium humidity can be raised/decreased by a given value by increasing/decreasing the specific gravity with a certain value without changing the kind of the thermoplastic resin.
Description
The application be that on 08 28th, 2007, application number are 200780001772.5 the applying date, denomination of invention divides an application for the application of " method that the method for moisture absorbent composition, moisture absorbent molding, control equilibrium humidity, control equilibrium humidity are held time ".
Technical field
The present invention relates to moisture absorbent composition and moisture absorbent molding, particularly have the moisture absorbent composition and the moisture absorbent molding of the humidity regulation function that can keep the humidity constant.The invention further relates to the method for control equilibrium humidity and the method that the control equilibrium humidity is held time.
Background technology
In fields such as food, medicine, electronic component or precision instrument, because causing oxidation etc., moisture absorption cause product quality to descend in order to prevent, use hygroscopic agent usually, for example silica gel, calcium chloride, quick lime and zeolite etc.Wrap up the hygroscopic agent of these particles or pulverulence with paper or nonwoven etc., perhaps be placed in the container, and put into packing with product.
On the other hand; For example; Patent document 1 (JP 07-53222B) and patent document 2 (JP07-96092B) suggestion provide moisture absorbent composition and moisture absorbent molding, and wherein concrete hygroscopic agent (for example, magnesium sulfate) is mediated in the thermoplastic resin; Show high-hygroscopicity and water holding capacity, and do not have for example dustability, hygroscopicity and because the defective of the leakage that deliquescence causes.
Simultaneously, in recent years, because various products are just being continually developed in the demand of product diversification or the development of manufacturing technology etc., therefore, tend to the variation of product storage condition etc.For example, cereal can chap when humidity is too low, on the contrary, enzymatic reaction infringement quality can take place when humidity is too high.Therefore, can be in the equilibrium humidity district (near RH 50%) environment of storing cereal be desirable storage condition.And then, for example water evaporates products such as tealeaves to a certain degree when moisture absorption causes humidity to raise, can go bad through enzymatic reaction or oxidation.Therefore, can be in the equilibrium humidity district environment of (near RH 20%) stored prod be desirable storage condition.
Yet for example silica gel, calcium chloride, quick lime and zeolite etc. often are used as the hygroscopic agent that hygroscopic agent uses, and have the physics and the chemical property of capable and experienced dry ability and moisture absorption.When these hygroscopic agents are placed in container or the bag etc. of sealing, absorb inner moisture in the hygroscopic agent short time, and continue to absorb moisture and reach 0% up to humidity.Therefore, conventional hygroscopic agent does not have the function of control moisture, and also has the problem that can not be suitable for storing more and more diversified product.
On the other hand, for example, patent document 3 (JP 05-39379A) has been advised the humidity regulation composition and the humidity regulation moulding article that have the humidity regulation function in the thermoplastic resin through concrete hygroscopic agent (magnesium sulfate) is mediated.
Mediate under the situation of the concrete hygroscopic agent of conduct in the thermoplastic resin at magnesium sulfate, the compound of resin and magnesium sulfate produces constant vapour pressure.But above-mentioned patent document 3 is paid close attention to the resin influence that vapour pressure in the case mediated, and the value that demonstrates when using the magnesium sulfate monomer is different.Therefore, the certain humidity that the kind through changing resin can appropriate control keeps.
That is, the specification of above-mentioned patent document 3 is based on and utilizes poisture-penetrability to change to depend on this fact of resin kind, the composition and the moulding article that obtain having different equilibrium humiditys through the kind that changes resin.Therefore, above-mentioned patent document 3 is not taken the proportion of resin self into account.This possibly be based on following reason.
Usually, gas infiltration capacity is confirmed through following formula: (gas infiltration capacity)=(gas permeability coefficient) * (draught head) * (area) * (time) ÷ (film thickness).Gas permeability (poisture-penetrability) is measured through the pressure differential in fixed, area, time and film thickness and is obtained.The gas permeability is a value, and gas permeability coefficient is depended in its variation, and general gas permeability coefficient is confirmed through following formula: (gas permeability coefficient)=(diffusion coefficient) * (solubility factor).Therefore; When the partial pressure difference with identical film thickness, area identical, identical time and same gas compared, the amount (gas infiltration capacity) of passing the gas of resin molding got into difficulty (solubility factor) and the product of gas mobile difficulty (diffusion coefficient) in film in the film for gas.
If confirmed the kind of gas, do not have very big variation even if changed the kind solubility factor of resin (polymer) yet, but along with the gas of predetermined polymer film changes and the significant variation of generation.
For same gas, diffusion coefficient marked change along with the kind of the resin (polymer) that forms polymer film, and with do not have quantitative relationship with gaseous species in the polymer film (that is, molecular size and molecular weight).
And then, though polymer tightly combine through hydrogen bond, have in the resin hydroxyl (OH) or amide groups (resin CONH-) is for water vapor sensitive.
When water entered into such resin, hydrogen bond was destroyed and disappears, and caused the molecular separating force of resin significantly to weaken.That is, water plastifies resin chain, and the gas permeability improves, and the motion of resin chain is activated.Therefore, gas spreads easily.When table 1 is represented the polymer absorption water of water sensitive, the increase of gas permeability (taking passages " the Food Packaging Handbook " that publish from Japan Packaging Institute).On the other hand; Have the polymer (PVC, PVCD and PET) of polymer (polyethylene and polypropylene) and the low polarity of hydrophobic structure, owing to interact polymer (PAN) with low gas permeability etc. of dipole has less water absorption, even and if when polymer contains water the gas permeability do not change yet.
Table 1
| | Condition | 25 ℃ of following O 2Permeability (note 1) | |
| Polyvinyl alcohol | Dry | 0.06 | |
| Polyvinyl alcohol | RH?95％ | 310 | |
| ? | ? | ? | |
| Glassine paper (uncoated material) | Dry | 2 | |
| ? | RH?100％ | 3，110 | |
| ? | ? | ? | |
| |
Dry | 18 | |
| |
RH?100％ | 78 | |
| ? | ? | ? | |
| Eval?F (note 2) | Dry | 0.26 | |
| Eval?F | RH?100％ | 31 | |
| ? | ? | ? | |
| PE | Dry | 7，510 | |
| PE | RH?100％ | 7，510 | |
| ? | ? | ? | |
| Polyacrylonitrile | Dry | 1.6 | |
| Polyacrylonitrile | RH?100％ | 1.7 |
(note 1) O
2Permeability: cc25.4 μ/m
224hr/atm
(note 2) Eval F is the copolymer of ethene and vinyl alcohol, and the content of therein ethylene alcohol is near 70%.
The O of the resin of the at present general usefulness of table 2 expression
2And H
2The O permeability (extracts is published from Japan Packaging Institute " Food Packaging Handbook ").Like clear demonstration the in the table, at O
2Permeability and H
2Have no relation between the O permeability, do not have outstanding feature.
Under the situation of gas permeability, diffusion is controlling elements, and under the situation of vapor permeation degree, the compatibility between water and the resin is a controlling elements.That is, hydrophobic resin often has low vapor permeation degree, and hydrophilic resin often has the high water vapor permeability.
Table 2
(note 1) O
2: cc25.4 μ/m
224hratm, RH 65%
H
2O：g/m
2·24hr·atm
As stated, gas permeability, particularly vapor permeation degree are the values that changes according to gas and resin kind.Therefore, be appreciated that into the difference in specific gravity of this value and resin irrelevant fully.Therefore, when routine obtains having composition and the moulding article of different equilibrium humiditys, do not consider the proportion of resin.
And then; Resin manufacture merchant's technical information (Sumitomo Chemical Co.; Ltd.; " Moisture vapor permeation rate of polyethylene film ", PE technical information III-4 is 1.) instruct out (sample: LDPE 60 μ-monofilm shown in figure 18; Measuring condition: 40 ℃, RH 90%), can infer that when having considered the difference in specific gravity of same resin, the resin with the big proportion of religion has less permeable degree.But, in conventional general technology general knowledge, think " need not consider proportion; " because because the difference of the permeable degree that the proportion difference causes is very little; And the difference in specific gravity of same resin does not have clear and definite relational expression, and difference in specific gravity do not produce big difference, therefore seldom considers the proportion of resin.
Under these circumstances, a kind of in the prior art resin can only be set an equilibrium humidity, and the kind that needs to change resin is to change certain humidity (equilibrium humidity) that will keep.
But; Manufactured goods with different choke character or physical property etc. need change the kind of resin; Under many circumstances; Be difficult to guarantee the organoleptic properties of the product that will store, or processing method is too complicated that cost and technology are had harmful effect, this causes being difficult to being formed for the problem of the suitable storage condition of highly diverse product.
Summary of the invention
The objective of the invention is to address the above problem and a kind of technology is provided; It is through mediating hygroscopic agent in the thermoplastic resin; Selection has the resin of the same race of different specific weight; Obtain having the moisture absorbent composition and the moisture absorbent molding of different equilibrium humiditys, and can easily form the environment that is suitable for storing more and more diversified product.
In order to address the above problem; According to a first aspect of the invention; Moisture absorbent composition comprises thermoplastic resin and hygroscopic agent, and said thermoplastic resin is selected from the group that following material is formed: polyethylene, polypropylene, PET, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, PBT, ABS, polyamide, polystyrene, polyvinyl alcohol, Merlon, ethylene-methyl acrylate copolymer, polyacetals, ethylene-vinyl acetate copolymer (ethylene-vinylacetate copolymer), polyacrylate, PLA, polyimides, methyl methacrylate, cellulose acetate and celluloid; Said hygroscopic agent has equilibrium vapour pressure, and it is mediated in the thermoplastic resin, and said hygroscopic agent is by formula MgSO
4NH
2The magnesium sulfate of O (0≤n≤3) expression is formed; Wherein the surface of hygroscopic agent scribbles fatty acid metal salts, and the secondary particle particle diameter that has when making hygroscopic agent be distributed in the thermoplastic resin is 1～40 μ m basically; At thermoplastic resin is under the condition of polyethylene, polypropylene, PET, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile or PBT; Proportion rising/reduction by 0.01 along with thermoplastic resin; Equilibrium humidity rises/decline RH 12% basically; And be under the situation of ABS, polyamide, polystyrene, polyvinyl alcohol, Merlon, ethylene-methyl acrylate copolymer, polyacetals, ethene-vinyl acetate=copolymer, polyacrylate, PLA, polyimides, methyl methacrylate, cellulose acetate or celluloid at thermoplastic resin; Along with the proportion rising/reduction by 0.01 of thermoplastic resin, equilibrium humidity rises/decline RH 3% basically.
Fatty acid metal salts can be a metallic soap.
The secondary particle particle diameter is essentially 0.0003～4 with the ratio of thermoplastic resin thickness.
According to the present invention includes second aspect, moisture absorbent composition comprises first thermoplastic resin or second thermoplastic resin and hygroscopic agent, and the poisture-penetrability of first thermoplastic resin is 0.1～50g/m
224hratm (40 ℃, RH 90%), the poisture-penetrability of second thermoplastic resin is 80～10000g/m
224hratm (40 ℃, RH 90%); Said hygroscopic agent has equilibrium vapour pressure, and it is mediated in the thermoplastic resin, and said hygroscopic agent is by formula MgSO
4NH
2The magnesium sulfate of O (0≤n≤3) expression is formed; Wherein the surface of hygroscopic agent scribbles fatty acid metal salts, and the secondary particle particle diameter that has when making hygroscopic agent be distributed in the thermoplastic resin is 1～40 μ m basically.
Under the situation of first thermoplastic resin; Proportion rising/reduction by 0.01 along with first thermoplastic resin; Equilibrium humidity can rise/decline RH 12% basically; And under the situation of second thermoplastic resin, along with the proportion rising/reduction by 0.01 of second thermoplastic resin, equilibrium humidity can rise/decline RH 3% basically.
According to a third aspect of the invention we, moisture absorbent molding comprises moisture absorbent composition.
According to a forth aspect of the invention, the method for equilibrium humidity may further comprise the steps in the control moisture absorbent composition: apply the surface of the hygroscopic agent with equilibrium vapour pressure with fatty acid metal salts, said hygroscopic agent is by formula MgSO
4NH
2The magnesium sulfate of O (0≤n≤3) expression is formed; And hygroscopic agent mediated in the thermoplastic resin, the secondary particle particle diameter that has when making hygroscopic agent be distributed in the thermoplastic resin is 1～40 μ m basically; Said thermoplastic resin is selected from the group that following material is formed: polyethylene, polypropylene, PET, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, PBT, ABS, polyamide, polystyrene, polyvinyl alcohol, Merlon, ethylene-methyl acrylate copolymer, polyacetals, ethylene-vinyl acetate copolymer, polyacrylate, PLA, polyimides, methyl methacrylate, cellulose acetate and celluloid; Wherein working as thermoplastic resin is under the situation of polyethylene, polypropylene, PET, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile or PBT; Proportion rising/reduction by 0.01 along with thermoplastic resin; Equilibrium humidity rises/decline RH 12% basically; And when thermoplastic resin is ABS, polyamide, polystyrene, polyvinyl alcohol, Merlon, ethylene-methyl acrylate copolymer, polyacetals, ethylene-vinyl acetate copolymer, polyacrylate, PLA, polyimides, methyl methacrylate, cellulose acetate or celluloid; Along with the proportion rising/reduction by 0.01 of thermoplastic resin, equilibrium humidity rises/decline RH 3% basically.
According to a fifth aspect of the invention, the method for holding time of equilibrium humidity may further comprise the steps in the control moisture absorbent composition: apply the surface of the hygroscopic agent with equilibrium vapour pressure with fatty acid metal salts, said hygroscopic agent is by formula MgSO
4NH
2The magnesium sulfate of O (0≤n≤3) expression is formed; And hygroscopic agent is mediated the secondary particle particle diameter that has when making hygroscopic agent be distributed in the thermoplastic resin in the thermoplastic resin is 1～40 μ m basically; Said thermoplastic resin is selected from the group that following material is formed: polyethylene, polypropylene, PET, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, PBT, ABS, polyamide, polystyrene, polyvinyl alcohol, Merlon, ethylene-methyl acrylate copolymer, polyacetals, ethylene-vinyl acetate copolymer, polyacrylate, PLA, polyimides, methyl methacrylate, cellulose acetate and celluloid; Thereby holding time of equilibrium humidity prolongs along with the increase (wt%) of the content of hygroscopic agent in thermoplastic resin.
According to the present invention, through hygroscopic agent being mediated in the moisture absorbent composition that obtains in the thermoplastic resin, mediating hygroscopic agent, to make the secondary particle particle diameter of the hygroscopic agent of dispersion be 1～40 μ m, and through selecting the specific gravity control equilibrium humidity of thermoplastic resin.Therefore, even similar resin also can be given different balance humidity easily.Therefore, when treating the suitable equilibrium humidity of stored prod, need not change the kind of resin, or to should changing the new processing method of research and remove harmful effect etc., and can easily form storage condition best for treating stored prod.
Other aspects of the present invention and advantage will be understood through the preferred implementation of following detailed description, through obtain best understanding with reference to accompanying drawing.
Description of drawings
Fig. 1 representes the measurement result of the equilibrium humidity of embodiment 1.
Fig. 2 representes the measurement result of the ability consumption rate of embodiment 2.
Fig. 3 representes the measurement result of the equilibrium humidity of embodiment 3.
Fig. 4 representes the measurement result of the ability consumption rate of embodiment 4.
Fig. 5 representes the measurement result of the equilibrium humidity of reference example (sample P).
Fig. 6 representes the measurement result of the equilibrium humidity of reference example (sample Q).
Fig. 7 representes the measurement result of the equilibrium humidity of embodiment 5.
Fig. 8 representes the measurement result of the equilibrium humidity of embodiment 6.
Fig. 9 is an enlarged drawing, the dispersity of the hygroscopic agent of its expression embodiment 7 (sample " a ").
Figure 10 is an enlarged drawing, the dispersity of the hygroscopic agent of its expression embodiment 7 (sample " a ").
Figure 11 is an enlarged drawing, the dispersity of the hygroscopic agent of its expression embodiment 7 (sample " b ").
Figure 12 is an enlarged drawing, the dispersity of the hygroscopic agent of its expression embodiment 7 (sample " b ").
Figure 13 is an enlarged drawing, the dispersity of the hygroscopic agent (sample " c ") of its expression embodiment 7.
Figure 14 is an enlarged drawing, the dispersity of the hygroscopic agent (sample " c ") of its expression embodiment 7.
Figure 15 is an enlarged drawing, the dispersity of the hygroscopic agent (sample " d ") of its expression embodiment 7.
Figure 16 is an enlarged drawing, the dispersity of the hygroscopic agent (sample " d ") of its expression embodiment 7.
Figure 17 is an enlarged drawing, the dispersity of the hygroscopic agent (sample " i ") of its expression embodiment 7.
Figure 18 representes the relation of resin proportion and poisture-penetrability.
The specific embodiment
The present invention is through the equilibrium humidity of the specific gravity control moisture absorbent composition of selection thermoplastic resin, and said moisture absorbent composition obtains through hygroscopic agent is mediated in the thermoplastic resin.The moisture absorbent composition that the present invention obtains can according to purposes easily machine-shaping be arbitrary form, for example film, thin slice, sheet material or further bag shape, ball shape or container etc.Gained moulding article this as hygroscopic agent, and can be used as packaging material.
For not restriction of thermoplastic resin, can use the known resin of the public, as long as this resin have two or more than selectable proportion grade.For example, can use in polyethylene, polypropylene, Merlon, polyamide, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, polyvinyl chloride, polystyrene, polyester, polyacrylate, polyvinylidene chloride, ABS, PLA, polyacetals, polyacrylonitrile, polyimides, the polyphenyl dioctyl phthalate fourth diester (PBT) a kind of, two or more.
Though the excursion of operable proportion depends on the basic proportion of thermoplastic resin, general scope be preferably 0.01 or more than, and more preferably 0.02 or above with abundant resolution gained equilibrium humidity.
Consider that from this angle for example, LLDPE, LDPE, ABS, PS or PA etc. are what be suitable for, and preferred especially LLDPE and ABS.In the resin in the market, LLDPE is especially suitable, but because its specific gravity range is wide and the converted products kind is many, and can further process through simpler method.
For example the specific gravity range of LLDPE is 0.900～0.930; The specific gravity range of ABS is 1.07～1.15; The specific gravity range of polyamide (nylon 6) is 1.09～1.17; Polyacrylic specific gravity range is 0.90～0.92, and the specific gravity range of polystyrene is 1.04～1.10, and the specific gravity range of polymethyl methacrylate resin is 1.17～1.20.The specific gravity range of vinyl chloride resin (hard) is 1.35～1.45; The specific gravity range of vinyl chloride resin (soft) is 1.15～1.70; The specific gravity range of vinylidene chloride is 1.7～1.8; The specific gravity range of polyvinyl alcohol is 1.17～1.18, the specific gravity range of cellulose acetate be 1.22～1.34 with the specific gravity range of celluloid be 1.35～1.40.Therefore, any resin may be used to the present invention.
Above-mentioned thermoplastic resin generally is divided into as shown in table 2 two groups technically.One group is the resin with good water proof barrier: polyethylene, polypropylene, PET, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile and polyphenyl dioctyl phthalate fourth diester (PBT), etc.Another group is the relatively poor resin of water proof barrier performance: ABS, polyamide, polystyrene, polyvinyl alcohol, Merlon, ethylene-methyl acrylate copolymer, polyacetals, ethylene-vinyl acetate copolymer, polyacrylate, PLA, polyimides, methyl methacrylate, cellulose acetate and celluloid etc.
Poisture-penetrability with thermoplastic resin (first thermoplastic resin) of good water proof barrier is 0.1～50, preferred 1～50g/m
224hratm (40 ℃, RH 90%).Poisture-penetrability to the relatively poor thermoplastic resin (second thermoplastic resin) of water proof barrier performance is 80～10000, preferred 80～3000g/m
224hratm (40 ℃, RH 90%).Table 3 show each resin that the file according to the past obtains poisture-penetrability (for example, TOYO KEIZAI INC. publishes " Hosozairyo no Jissaichishiki, 2nd Ed. (Practical knowledge of packaging materials) ").
Table 3
(note 1) g/m
224hratm (40 ℃, RH90%)
Numerical value is scaled resin thickness 25 μ m.
A key character of the present invention is the equilibrium humidity through the specific gravity control moisture absorbent composition of selecting thermoplastic resin.
The term proportion of thermoplastic resin " select " refers to through from two kinds of thermoplastic resin or above proportion rank, selecting predetermined proportion to utilize resin.
When the material that will have equilibrium vapour pressure (hygroscopic agent) was mediated in the resin, the composition that resin and hygroscopic agent form received the influence of resin, shows and independent hygroscopic agent material different balance vapour pressure.The dividing potential drop of the vapour pressure of the composition that resin and hygroscopic agent form and the steam partial pressure balance of external environment, this is called equilibrium vapour pressure, and the relative humidity that indicated by steam partial pressure this moment is called " equilibrium humidity ".
" equilibrium humidity " that offer moisture absorbent composition of the present invention treated the optimum humidity (relative humidity) of stored article (for example commodity and product) based on storage; Said thus article can show the original performance of article, and can corresponding article to be stored and concrete the setting.Such optimum humidity is treated stored article and difference according to different, but is generally RH 10%～RH 60%.Above-mentioned " equilibrium humidity " preferably optimum humidity ± 10% scope in, and more preferably in ± 5% scope.If equilibrium humidity in such scope, can form the storage condition that is particularly suitable for treating stored article.
" control equilibrium humidity " means " equilibrium humidity " remained on moisture absorbent composition due " equilibrium humidity ".According to the seasonal factor etc. during raw material control range or the processing, treat that the optimum humidity of stored article has certain limit.If it is too small that the scope of " equilibrium humidity " controls to, need several kinds of compositions (moulding article) to handle a kind of stored article of treating, therefore, the selection of the control of product and packaging material etc. are too complicated, and are therefore not preferred.
Wait to mediate hygroscopic agent in the thermoplastic resin and be preferably and have equilibrium vapour pressure (equilibrium humidity) and absorb the anhydride of the material of the crystallization water, can use for example magnesium sulfate, copper sulphate, cobalt chloride, calcium chloride or magnesium chloride etc.Consider the superiority of state (not having deliquescence etc.) or the heat endurance etc. of dispersiveness in resin, moisture absorption efficient, the final step of moisture absorption, by formula MgSO
4NH
2The magnesium sulfate, particularly anhydrous magnesium sulfate of O (0≤n≤3) expression are very suitable.
When mediating in the resin, because the heat that produces in mediating, the Magnesium sulfate heptahydrate that surpasses three hydrations discharges its hydrate water, and hinders and produce.The humidity regulation composition of effective efficiency can not be obtained to show, even when attempting, the moulding article of sales value can not be obtained by said composition manufacturing moulding article (for example film, thin slice and container).If use anhydrous magnesium sulfate; Accomplish temperature province (100 ℃～400 ℃) at resin, the moisture releasing amount in the processing (moisture desorption) reduces, and can improve the hygroscopic capacity in the moulding article; Because it is heat endurance very high (work in-process does not decompose), thereby preferred especially.
Hereinafter, be that concrete embodiment explains the effect of mediating the hygroscopic agent in the thermoplastic resin with magnesium sulfate.
When the used magnesium sulfate of the present invention began to absorb moisture under the steady temperature condition, vapour pressure increased along with the hydration stage development.Relevant therewith, reduce with the differing from of dividing potential drop of Environmental Water steam, therefore, hydroscopicity descends.The composition that as a result, can obtain to keep certain humidity and have the humidity regulation function.And then, when the used magnesium sulfate of the present invention absorbs moisture, produce hexahydrate.Then, along with the increase of moisture absorption only increases hexahydrate, and do not produce one to pentahydrate simultaneously.At this moment, when the amount of anhydrous magnesium sulfate can be ignored, that is, suction reaches 43～48%, and hexahydrate becomes heptahydrate.According to this fact, anhydride exists under high moisture absorption, and unlike utilizing other hydrates to form the hygroscopic agent of salt, therefore, hygroscopic agent of the present invention becomes the composition that keeps the hygroscopicity constant and have the humidity regulation function.
And then the used magnesium sulfate self of the present invention shows constant vapour pressure, and can moisture absorption, up to dividing potential drop and self vapour pressure balance of Environmental Water steam.When mediating above-mentioned magnesium sulfate in the resin, the compound of magnesium sulfate and resin shows certain vapour pressure.The vapour pressure independent with magnesium sulfate is different, and the vapour pressure of this moment has been mediated the influence of poisture-penetrability of the resin of magnesium sulfate, and has different values according to resin.And then, in the present invention, find can the vapour pressure of being paid close attention to be controlled to different values through the resin of in resin of the same race, selecting to have different specific weight.In this case, the point that causes balance is different naturally, and the equilibrium humidity during moisture absorption is also different again.Therefore, can control certain humidity to be kept (equilibrium humidity) through the proportion of suitably selecting resin.
Hygroscopic agent is change of size little (perhaps and do not change) before and after moisture absorption preferably.Reason is when expanding after the hygroscopic agent moisture absorption, and moulding article itself expand, and make the shape that can not keep product.
And then because some factors (for example charged, moisture absorption and pressure), hygroscopic agent produces the reunion material in air.But in the present invention, the secondary particle of hygroscopic agent maintains predetermined size, and as far as possible evenly disperses in the stage of hygroscopic agent being mediated in the resin.
In order to utilize the specific gravity range grade difference performance (equilibrium humidity) of resin, more specifically, the secondary particle particle diameter of hygroscopic agent preferably is made as 1～40 μ m basically when mediating and being distributed in the resin.Particularly, average grain diameter preferably is made as about 20 μ m, and maximum particle diameter to deduct the smallest particles particle diameter be about 30 μ m.Therefore, the particle diameter of hygroscopic agent primary particle preferably is made as about 1～30 μ m, and about 4～6 μ m of average grain diameter.
The effective thickness of the thermoplastic resin of treating to mediate with hygroscopic agent is generally 10 μ m～3mm.The secondary particle particle diameter preferably is 0.0003～4 with the ratio of the thickness of the thermoplastic resin that has disperseed hygroscopic agent basically, and more preferably is 0.0004～1 basically.When the ratio of paying close attention in this scope and the secondary particle particle diameter of hygroscopic agent also in said scope the time, thermoplastic resin can fully apply hygroscopic agent, and it makes and can obtain effect of the present invention more reliably.
Hygroscopic agent (for example, magnesium sulfate) is easy to generate the aggregate of consolidation, and it is difficult to as discuss the front, disperse.But, usually, can not notice in the stage that hygroscopic agent is mediated and is distributed in the resin secondary particle is processed certain small particle diameter.Therefore, even if in the primary particle stage, the particle diameter of hygroscopic agent is reunited in kneading near 1～40 μ m easily, and the maximum bulk that produces the hundreds of micron.
Therefore, obtain in resin, being dispersed with the composition and the moulding article of such aggregate.But, under such dispersity, causing in the interface of the resin bed of mediating hygroscopic agent, the secondary particles of a lot of thick hygroscopic agents stretch out and are not included in the part in the resin bed.
Secondary particle at hygroscopic agent is included in the part in the resin bed, and particle diameter difference is excessive, and resin layer surface is different to the distance between the hygroscopic agent of mediating.Therefore, the wettability power of the hygroscopic agent in the resin changes.
In this case, the performance of the hygroscopic agent in the resin is inhomogeneous, and is not can be with the state of resin difference in specific gravity explanation performance difference.
The objective of the invention is to when hygroscopic agent is mediated and is distributed in the thermoplastic resin, the secondary particle particle diameter of hygroscopic agent has uniformity.Through suppressing moisture absorption and making meticulous primary particle, be difficult to form aggregate.Even if the formation aggregate, aggregate is also disintegrated easily.And, the kneading stage through improving the affinity between resin Composition and hygroscopic agent, and hygroscopic agent is mediated in the resin with the state that is easier to adapt to, disperse secondary particle through particle diameter being remained on equably 1～40 μ m.For this reason, (for example surfactant-based dispersant fatty acid metal salts such as (for example) metallic soaps applies the surface of hygroscopic agent preferably to use the material high with the compatibility of resin.
More particularly, hygroscopic agent is compound with fatty acid metal salts under the temperature conditions more than the fatty acid metal salts fusing point, and ratio is 15 weight portions or above fatty acid metal salts: 100 weight portion hygroscopic agents.As a result, the surface of hygroscopic agent scribbles fatty acid metal salts.
Secondary particle particle diameter through with the hygroscopic agent that disperses controls to preliminary dimension, and thermoplastic resin can apply hygroscopic agent fully, and resin surface is to the basic homogeneous of the distance of hygroscopic agent.Therefore, only obtaining to utilize a shade of difference performance (equilibrium humidity) of resin difference in specific gravity under such dispersity.
When the secondary particle of hygroscopic agent from mediating the resin surface projection during not by resin-coated, particle is not influenced by resin, but in equilibrium humidity (the being RH 4% during anhydrous magnesium sulfate) moisture absorption of hygroscopic agent self.When disperseing bad hygroscopic agent to increase, it is less that hygroscopic agent receives the resin influence, and depend on respect to receive the ratio of the hygroscopic agent part of resin influence, and the equilibrium humidity the when equilibrium humidity of whole composition applies the hygroscopic agent particle fully with resin is significantly different.And then the performance of composition is not a constant, and each production receives influences such as dispersion condition, and forms the product with different performance.
Mediate in the processing in the thermoplastic resin at hygroscopic agent, hygroscopic agent and resin become fluidized state.Possibly be because the difference of flowability on both sides, because with the inner surface of pipeline friction etc., corase particles tends to rise from resin surface.Test observation according to the inventor, when the secondary particle particle diameter of hygroscopic agent surpasses about 40 μ m, this tendency becomes main flow; And it is, particularly, very clear as the about 30 μ m of secondary particle particle diameter or when following; All particles are fully by resin-coated, even if particle can be dispersed near the resin surface.
In the present invention, raw material to be mediated partly is about 5～400 weight portion hygroscopic agents: 100 weight portion thermoplastic resins, and can suitably change according to the application of composition.When the hygroscopic agent part was in above-mentioned scope, the decentralization of hygroscopic agent in resin was satisfactory, and shows high-hygroscopicity and water retention property.And then, obtain having the moisture absorbent composition of excellent forming ability.
Except above-mentioned thermoplastic resin and hygroscopic agent, can suitably add predetermined blowing agent and additive to moisture absorbent composition of the present invention, only otherwise influence the object of the invention.As blowing agent, for example can use azo isobutyronitrile, azodicarbonamide or 4,4 '-oxybenzene sulfohydrazide (4; 4 '-oxybenzene sulfonyl hydrazide) etc.; And as additive, can use public's known additives, for example plasticizer, stabilizing agent, lubricant and colouring agent.
Method for making moisture absorbent composition of the present invention has no particular limits, and composition usually can be in order to the below manufactured.That is, thermoplastic resin, hygroscopic agent and other additives were mediated about 5～40 minutes with mixing mill etc. at 100～350 ℃.But, produce the preferred processing equipment that has a gratifying dispersibility in the granulation stage that utilizes especially and carry out in order to obtain high dispersive and high concentration particle (pellet, down with).
Use composition that said method obtains to be arbitrary form through machine-shapings such as extrusion modling, coextruded profiled, injection mo(u)lding, hollow molding, extrusion coated moulding or crosslinked foams moulding.Composition can also form layered product, and the words that wherein need can range upon range of other laminated materials.For laminated material, except resin, can also use paper, fiber, metal, various coating material, various binding agent and have the moisture absorbent molding of the present invention of different components such as above-mentioned thermoplastic resin.
Use these particles, obtain having the three layer expanded film (LLDPE 20 μ m/s trial-production particle 30 μ m/LLDPEs 10 μs) of the particle of LLDPE skin, above-mentioned trial-production as intermediate layer, LLDPE internal layer through expansion molding machinery.
Next, with pressure roller above-mentioned three layers of expanded film and polyethylene film and aluminium foil are done lamination process and obtain the thick sheet material of 0.81mm (PET 12 μ m/D/AL 9 μ m/D/LLDPE 20 μ m/ trial-production particle 30 μ m/LLDPE 10 μ m; D is dried laminate layers).Then, this sheet material is processed into the packaging bag of A4 size (volume 2.4L), as sample A.
With 100 weight portion LLDPE (LLDPE) (proportion 0.920); 50 weight portion anhydrous magnesium sulfates (the average primary particle diameter is 4～6 μ m) mix; With the similar manner of preparation sample A, the trial-production particle obtains three layers of expanded film (LLDPE 20 μ m/ trial-production particle 30 μ m/LLDPE 10 μ m) then.Through when mediating, adding fatty acid metal salts, make the magnesium sulfate surfaces coated be covered with fatty acid metal salts.The secondary particle particle diameter of the magnesium sulfate that disperses is made as 1～40 μ m (average 10～20 μ m).The weight ratio of magnesium sulfate and fatty acid metal salts is 100/15.
Then, A is similar with sample, obtains sheet material (PET 12 μ m/D/AL 9 μ m/D/LLDPE 20 μ m/ trial-production particle 30 μ m/LLDPE10 μ m with three layers of expanded film and polyethylene film and aluminium foil laminate processing; D is dried laminate layers).This sheet material is processed into the packaging bag of sample A size, as sample B.
In addition, among sample A and the sample B, place identical LLDPE plate (proportion 0.922) in trial-production particle both sides.
Above-mentioned sample A and B are used as specimen, and under 25 ℃ of conditions of steady temperature, in each bag, load onto the temperature and humidity detector, begin moisture absorption to measure equilibrium humidity from RH 100% then.After reaching equilibrium humidity, get back to RH 100% lay equal stress on revert to take drugs wet to measure.
The result is shown in Fig. 1.
Like clear demonstration among Fig. 1, the equilibrium humidity of sample A is RH16～17%, and the equilibrium humidity RH29 of sample B～30%.Therefore, even if the content of magnesium sulfate is identical,, also can obtain the different moisture absorbent composition of equilibrium humidity through selecting to have the resin that the LLDPE conduct is treated and magnesium sulfate is mediated of different specific weight.In this embodiment, the LLDPE difference in specific gravity is that 0.011 equilibrium humidity difference is RH13～14%, and the lower LLDPE of proportion is than keeping balance under the low humidity.In other words, very clear, LLDPE proportion increase/minimizing 0.01, the then about RH12% of equilibrium humidity rising/reduction.
According to present embodiment, can control the equilibrium humidity that will provide easily through the LLDPE that selects suitable proportion.Therefore, can obtain suitable storage condition according to article to be stored.
For example; Packaging bag with composition of sample A of the present invention is effective to use medicine or the diagnosticum of antibody or enzyme and soft capsule to wait for stored article, and the packaging bag with composition of sample B of the present invention is effective to absorb medicine and soft capsule (having approaching equilibrium humidity) wait stored article through skin.Therefore, need to change the best storage condition of kind to support that formation is such of resin.But,, can obtain being suitable for treating the equilibrium humidity of stored article through the specific gravity control that changes resin according to article to be stored according to present embodiment.
Three layers of expanded film that embodiment 1 sample A makes in producing (LLDPE 20 μ m/ trial-production particle 30 μ m/LLDPE 10 μ m) are as sample C.
Three layers of expanded film that embodiment 1 sample B makes in producing (LLDPE 20 μ m/ trial-production particle 30 μ m/LLDPE 10 μ m) are as sample D.
As specimen, and place 25 ℃ of steady temperatures, constant humidity to be respectively under three kinds of conditions of RH 20%, 50% and 75% with above-mentioned sample C and D.Measure weight change then.Fig. 2 shows the measurement result of representing with the ability consumption rate.
The ability of hygroscopic agent is generally represented (recruitment multiply by 100 (%) divided by original weight value) with hydroscopicity under many circumstances, but according to the amount of absorbent or or even the moisture absorption layer of same thickness in the structure of other layers, hydroscopicity can be different.Therefore, in this embodiment, the maximum capacity that can provide composition and moulding article is considered to 100%, shows that with the ability consumption rate consumption situation is convenient to comparison.
Fig. 2 observes ability consumption state under RH 20% condition, and sample C weight changes, and shows the consumption of having the ability, but sample D does not from start to finish have weight change, and does not show ability consumption.Because the environment in this test is the condition of constant humidity, this test shows can be equal to or less than environmental condition in the equilibrium humidity (limit of sample moisture absorption) of the sample of this environment moisture absorption.On the contrary, can not be equal to or higher than environmental condition in the equilibrium humidity (limit of sample moisture absorption) of the sample of this environment moisture absorption.
As a result, the equilibrium humidity of sample C is lower than RH 20%, and the equilibrium humidity of sample D is RH20～50%.Therefore, be appreciated that and be that sample C and D show different balance humidity.
Present embodiment is also supported: even if the content of magnesium sulfate is identical, through selecting to have the resin that the LLDPE conduct is treated and magnesium sulfate is mediated of different specific weight, can obtain the different moisture absorbent composition of equilibrium humidity.
100 weight portion LDPE (low density polyethylene (LDPE)) (proportion 0.922), 150 weight portion anhydrous magnesium sulfates (the average primary particle diameter is 4～6 μ m) are mixed; Be similar to embodiment 1 then, the trial-production particle obtains three layers of expanded film (LDPE 20 μ m/ trial-production particle 30 μ m/LDPE 10 μ m).Through when mediating, adding fatty acid metal salts, make the magnesium sulfate surfaces coated be covered with fatty acid metal salts.The secondary particle particle diameter of the magnesium sulfate that disperses is made as 1～40 μ m (average 10～20 μ m).The weight ratio of magnesium sulfate and fatty acid metal salts is 100/15.
Then, be similar to embodiment 1, obtain sheet material (PET 12 μ m/D/AL 9 μ m/D/LDPE 20 μ m/ trial-production particle 30 μ m/LDPE 10 μ m with three layers of expanded film and polyethylene film and aluminium foil laminate; D is dried laminate layers).This sheet material is cut into 21cm * 30cm size obtains sample E.
100 weight portion LDPE (proportion 0.922), 50 weight portion anhydrous magnesium sulfates (the average primary particle diameter is 4～6 μ m) are mixed, be similar to sample E then, the trial-production particle obtains three layers of expanded film (LDPE 20 μ m/ trial-production particle 30 μ m/LDPE 10 μ m).Through when mediating, adding fatty acid metal salts, make the magnesium sulfate surfaces coated be covered with fatty acid metal salts and apply.The secondary particle particle diameter of the magnesium sulfate that disperses is made as 1～40 μ m (average 10～20 μ m).The weight ratio of magnesium sulfate and fatty acid metal salts is 100/15.
Then, be similar to sample E, obtain sheet material (PET 12 μ m/D/AL 9 μ m/D/LDPE 20 μ m/ trial-production particle 30 μ m/LDPE 10 μ m with three layers of expanded film and polyethylene film and aluminium foil laminate; D is dried laminate layers).This sheet material is processed into the size identical with sample E obtains sample F.
Above-mentioned sample E and F place other glass container of branch (volume 0.9L) as specimen.Under 25 ℃ of conditions of steady temperature, in each container, load onto the temperature and humidity detector then, begin moisture absorption to measure equilibrium humidity from RH 100% then.After reaching equilibrium humidity, get back to RH 100% lay equal stress on revert to take drugs wet to measure.The result is shown in Fig. 3.
Like clear demonstration among Fig. 3, sample E and F have essentially identical equilibrium humidity, are respectively RH26～29%.
Therefore, even if the content of magnesium sulfate changes, but when the proportion of the resin LDPE that treats to mediate with magnesium sulfate was identical, moisture absorbent composition had roughly the same equilibrium humidity.
Three layers of expanded film that embodiment 3 sample E make in producing (LDPE 20 μ m/ trial-production particle 30 μ m/LDPE 10 μ m) are as sample G.
Three layers of expanded film that embodiment 3 sample F make in producing (LDPE 20 μ m/ trial-production particle 30 μ m/LDPE 10 μ m) are as sample H.
Above-mentioned sample G and H be as specimen, and place 25 ℃ of steady temperatures, constant humidity to be respectively under three kinds of conditions of RH 20%, 50% and 75%.Measure weight change then.Fig. 4 shows the measurement result of representing with the ability consumption rate.
Show that as Fig. 4 is clear sample G and H are non-hygroscopic when ambient humidity is RH 20%, still moisture absorption and consume its ability when ambient humidity is RH 50%.Though, the process of ability consumption rate (progress time) difference, moisture absorption shows identical situation with non-hygroscopic, and it shows that equilibrium humidity (hygroscopic limits of two samples) all is higher than RH 20%, and is lower than RH 50%.
Present embodiment is also supported: even if the content of magnesium sulfate, but wait that the resin LDPE that mediates magnesium sulfate has equal specific gravity, equilibrium humidity does not almost have difference.
Reference example
100 weight portion LDPE (low density polyethylene (LDPE)) (proportion 0.920), 150 weight portion anhydrous magnesium sulfates (the average primary particle diameter is 4～6 μ m) are mixed; Be similar to embodiment 1 then, the trial-production particle obtains three layers of expanded film (LDPE 20 μ m/ trial-production particle 30 μ m/LDPE 10 μ m).For the dispersity of magnesium sulfate, do not control the management that secondary particle diminishes, and contain 30% thick secondary particle (particle diameter about greater than 40 μ m and less than the scope of about 100 μ m).In brief, the surface of magnesium sulfate is not coated with fatty acid metal salt.
Next, with pressure roller above-mentioned three layers of expanded film and polyethylene film and aluminium foil are done lamination process and obtain the thick sheet material of 0.81mm (PET 12 μ m/D/Al 9 μ m/D/LDPE 20 μ m/ trial-production particle 30 μ m/LDPE 10 μ m; D is dried laminate layers).Then, this sheet material is processed into the packaging bag (volume 2.4L) of A4 size, as sample P.
And then, will manufacture experimently particle through injection mo(u)lding and process sheet material (85mm * 54mm, 1.5mm is thick) as sample Q.
Above-mentioned sample P is used as specimen, and under 25 ℃ of conditions of steady temperature, in bag, loads onto the temperature and humidity detector, begins moisture absorption to measure equilibrium humidity from RH 100% then.After reaching equilibrium humidity, get back to RH 100% lay equal stress on revert to take drugs wet to measure.The result is shown in Fig. 5.
Above-mentioned sample Q places glass container (volume 0.9L) as specimen.Under 25 ℃ of conditions of steady temperature, in container, load onto the temperature and humidity detector then, begin moisture absorption to measure equilibrium humidity from RH 100% then.After reaching equilibrium humidity, get back to RH 100% lay equal stress on revert to take drugs wet to measure.The result is shown in Fig. 6.
Like clear demonstration the in Fig. 5 and 6, sample P shows that with Q initial balance humidity is about RH 20%, but moisture absorption afterwards descends, and demonstration is equilibrated at that to be equal to or higher than RH 30% place reciprocal.When the secondary particle particle diameter of magnesium sulfate was 1～40 μ m, the specimen expection showed that stably equilibrium humidity is about 30%, but above-mentioned measurement all obtains remarkable unsettled equilibrium humidity at every turn.
The corase particles moisture absorption of the magnesium sulfate that this phenomenon seemingly exists owing to resin surface and do not receive that the influence of resin causes, and initial equilibrium humidity is whole descends.Be thought of as, for the second time or for the second time during moisture absorption, corase particles has lost wettability power, and the magnesium sulfate particle that equilibrium humidity is only scribbled resin influences.
Therefore, when containing the secondary particle particle diameter and surpass the magnesium sulfate corase particles of 40 μ m, process composition and article shaped with two or more equilibrium humidity grades.This situation changes along with the content of corase particles or the thickness of moulding article etc., is difficult to obtain having the product of stability.Therefore, can not give different balance humidity through the small degree difference of resin difference in specific gravity.
100 weight portion ABS (proportion 1.05), 50 weight portion anhydrous magnesium sulfates (the average primary particle diameter is 4～6 μ m) are mixed, be similar to embodiment 1 then, the trial-production particle.Through when mediating, adding fatty acid metal salts, make the magnesium sulfate surfaces coated be covered with fatty acid metal salts and apply.The secondary particle particle diameter of the magnesium sulfate that disperses is made as 1～40 μ m (average 10～20 μ m).The weight ratio of magnesium sulfate and fatty acid metal salts is 100/15.
Make sheet material (54mm * 84mm, 2mm is thick) as sample I through these particles of use in injection molding.
100 weight portion ABS (proportion 1.01), 50 weight portion anhydrous magnesium sulfates (the average primary particle diameter is 4～6 μ m) are mixed, be similar to embodiment 1 then, the trial-production particle.Through when mediating, adding fatty acid metal salts, make the magnesium sulfate surfaces coated be covered with fatty acid metal salts.The secondary particle particle diameter of the magnesium sulfate that disperses is made as 1～40 μ m (average 10～20 μ m).The weight ratio of magnesium sulfate and fatty acid metal salts is 100/15.
Make plate (54mm * 84mm, 2mm is thick) as sample J through these particles of use in injection molding.
Above-mentioned sample I and J be as specimen, and two plates of sample of the same race are placed other glass container of branch (volume 0.9L) respectively.Next, under 25 ℃ of conditions of steady temperature, in each container, load onto the temperature and humidity detector, begin moisture absorption to measure equilibrium humidity from RH 100% then.After reaching equilibrium humidity, get back to RH 100% lay equal stress on revert to take drugs wet to measure.The result is shown in Fig. 7.
Shown in Fig. 7 was clear, the equilibrium humidity of sample I was RH20～21%, and the equilibrium humidity of sample J is RH8～9%.
Though, in sample I, in the 1st, 2 and 3 time is measured; The difference of equilibrium humidity is about RH10%; But at thickness big and surface area little in, just in sample, observe this phenomenon, this is because moisture absorption is carried out on the surface earlier; Develop into sample interior gradually, this development has postponed to reach balance time.That is, equilibrium humidity does not raise, but decrease speed is slack-off.If with longer time image data, equilibrium humidity can drop to can be with first or the balance (RH20～21%) of secondary equilibrium phase ratio.
Therefore, be similar to embodiment 1, can obtain demonstrating the moisture absorbent composition of different balance humidity as the proportion of the ABS that mediates magnesium sulfate through selecting different proportion.In the present embodiment, equilibrium humidity difference RH11～13%th caused by the difference in specific gravity 0.04 of ABS, and the lower ABS of proportion is than balance under the low humidity.In other words, very clear, along with ABS proportion increase/minimizing 0.01, the about RH3% of equilibrium humidity rising/reduction.
In the present embodiment; Carry out the test similar with sample E among the embodiment 3 and F, and observe in ability initial stage (early stage of capability) and 50% consumption stage of ability (stage of capability consumption of 50%) and realize equilibrium humidity with embodiment 3.This result is shown in Fig. 8.
Shown in Fig. 8 was clear, the time that the higher sample E of magnesium sulfate content (wt%) reaches equilibrium humidity was shorter than sample F.And then generally speaking, equilibrium humidity has definite value, and tending to increases and improve along with ability consumption in scope.But even if moisture absorption development and ability consumption also develop, sample E can keep and equilibrium humidity like the preliminary phase for a long time.
Therefore, even if ability consumes the stage owing to the amount that has increased as the magnesium sulfate of hygroscopic agent develops, still can restrain the increase of equilibrium humidity, and keep for a long time and the essentially identical value of the equilibrium humidity of initial stage.On the contrary, keep the time of initial stage equilibrium humidity to shorten through reducing hygroscopic agent content.
That is, very clear, when hygroscopic agent in predetermined following time of dispersity, keep the time of equilibrium humidity and can control through the content that changes hygroscopic agent.Only just obtain later in the big dispersity of secondary particle of having improved hygroscopic agent through the present invention.
In the present embodiment, the dispersion situation through electron microscope observation prior art hygroscopic agent, used the dispersion situation of the hygroscopic agent of the present invention of sample " a "～" j " to measure and analyze.
Table 4 shows measurement result and the measurement result and the ratio (beta/alpha) thereof of the secondary particle particle diameter of the measurement result of resin (α) (moisture absorption layer) thickness of having mediated hygroscopic agent, hygroscopic agent (β) is described.And then Fig. 9～Figure 17 is presented at the representative instance in the enlarged photograph of dispersion situation of the hygroscopic agent that shows each sample.
Table 4
In above-mentioned explanation, sample " a " is made according to prior art with " b ", and the secondary particle particle diameter of hygroscopic agent is not controlled at preliminary dimension, and the surface of magnesium sulfate is not coated with fatty acid metal salt.Sample " c "～" j " is constructed in accordance, and the secondary particle particle diameter of hygroscopic agent is controlled in the preliminary dimension, and the surface of hygroscopic agent scribbles fatty acid metal salts.
The following condition of each sample evidence forms, and as hygroscopic agent, and the thickness of moisture absorption layer is design load with anhydrous magnesium sulfate.
-sample a
(moisture absorption layer: LDPE (proportion 0.922) basic unit (base), hygroscopic agent content (wt%, down together) 33%)
-sample b
(moisture absorption layer: LDPE (proportion 0.920) basic unit, hygroscopic agent content 33%)
-sample c
(moisture absorption layer: LDPE (proportion 0.922) basic unit, hygroscopic agent content 33%)
-sample d
(moisture absorption layer: LDPE (proportion 0.922) basic unit, hygroscopic agent content 33%)
-sample e
Moisture absorption layer, individual layer 50 μ
(moisture absorption layer: LDPE (proportion 0.922) basic unit, hygroscopic agent content 33%)
-sample f
Moisture absorption layer, individual layer 60 μ (moisture absorption layer: LLDPE (proportion 0.909) basic unit, hygroscopic agent content 33%)
-sample g
Moisture absorption layer, individual layer 1.5mm
(moisture absorption layer: LLDPE (proportion 0.909) basic unit, hygroscopic agent content 33%)
-sample h
Moisture absorption layer, individual layer 2.5mm
(moisture absorption layer: LDPE (proportion 0.922) basic unit, hygroscopic agent content 33%)
-sample i
Moisture absorption layer, individual layer 1.5mm
(moisture absorption layer: ABS (proportion 1.05) basic unit, hygroscopic agent content 33%)
-sample j
Moisture absorption layer, individual layer 2.5mm
(moisture absorption layer: ABS (proportion 1.05) basic unit, hygroscopic agent content 33%)
Fig. 9～Figure 17 shows that in the sample " a " and " b " of prior art, the particle of observing magnesium sulfate breaks through moisture absorption layer, stretches out the surface.On the other hand, in sample of the present invention " c "～" j ", the particle of the magnesium sulfate of all samples is included in the moisture absorption layer.
Table 3 is clear to show that in sample of the present invention " c "～" j ", the particle diameter of magnesium sulfate (secondary particle particle diameter) is 1～30 μ m.Magnesium sulfate particle diameter (secondary particle particle diameter) is maximum 0.4, minimum 0.00192 with the ratio of resin bed (moisture absorption layer) thickness.
But in sample " c "～" j ", kneading and the dispersion of magnesium sulfate in resin carried out through same method.Therefore, according to estimates, in sample " c " with minimum thick resin film (30 μ m); Particle diameter is that the magnesium sulfate of about 30 μ m is disperseed; And similarly, in the sample with maximum thick resin film (2.6mm) " h ", particle diameter is that the magnesium sulfate of about 1 μ m is disperseed.Therefore, in the present embodiment, have the resin bed (moisture absorption layer) of magnesium sulfate particle diameter (secondary particle particle diameter) and the ratio estimate maximum of film thickness and be about 1 (=30 μ m/30 μ m), minimum is about 0.00038 (=1 μ m/2.6mm).
The invention provides the technology of being convenient to form the condition of storage that is suitable for the highly diverse product.That is,, obtain different balance humidity through selecting the resin proportion in the resin of the same race through hygroscopic agent being mediated in the moisture absorbent composition and moisture absorbent molding that obtains in the thermoplastic resin.Therefore, the present invention can be used for various fields such as food, electronic component or precision instrument, and has industrial applicibility.
To those skilled in the art, be conspicuous for a lot of changes on the preferred implementation details of the invention described above.Therefore, scope of the present invention should be limited the following claim book.
Claims (7)
1. moisture absorbent composition, it comprises:
Thermoplastic resin, it is selected from the group that following material is formed: polyethylene, polypropylene, PET, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, PBT, ABS, polyamide, polystyrene, polyvinyl alcohol, Merlon, ethylene-methyl acrylate copolymer, polyacetals, ethylene-vinyl acetate copolymer, polyacrylate, PLA, polyimides, methyl methacrylate, cellulose acetate and celluloid; With
Hygroscopic agent with equilibrium vapour pressure, it is mediated in the thermoplastic resin, and said hygroscopic agent is by formula MgSO
4NH
2The magnesium sulfate that O representes is formed, in the formula, and 0≤n≤3; Wherein
The surface of hygroscopic agent scribbles fatty acid metal salts, and the particle diameter of the secondary particle that has when making hygroscopic agent be dispersed in the thermoplastic resin is 1～40 μ m,
At thermoplastic resin is under the situation of polyethylene, polypropylene, PET, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile or PBT, along with the proportion rising/reduction by 0.01 of thermoplastic resin, and equilibrium humidity rising/decline RH 12%, and
At thermoplastic resin is under the situation of ABS, polyamide, polystyrene, polyvinyl alcohol, Merlon, ethylene-methyl acrylate copolymer, polyacetals, ethene-vinyl acetate ester copolymer, polyacrylate, PLA, polyimides, methyl methacrylate, cellulose acetate or celluloid; Along with the proportion rising/reduction by 0.01 of thermoplastic resin, equilibrium humidity rising/decline RH 3%.
2. moisture absorbent composition according to claim 1, wherein, said fatty acid metal salts is a metallic soap.
3. moisture absorbent composition according to claim 1 and 2, wherein, said secondary particle particle diameter is 0.0003～4 with the ratio of thermoplastic resin thickness.
4. moisture absorbent composition, it comprises:
A kind of in first thermoplastic resin and second thermoplastic resin, under 40 ℃, the condition of RH 90%, the poisture-penetrability of first thermoplastic resin is 0.1～50g/m
224hratm, the poisture-penetrability of second thermoplastic resin is 80～10000g/m
224hratm; With
Hygroscopic agent with equilibrium vapour pressure, it is mediated in the thermoplastic resin, and said hygroscopic agent is by formula MgSO
4NH
2The magnesium sulfate that O representes is formed, in the formula, and 0≤n≤3; Wherein
The surface of hygroscopic agent scribbles fatty acid metal salts, and the secondary particle particle diameter that has when making hygroscopic agent be dispersed in the thermoplastic resin is 1～40 μ m.
5. moisture absorbent composition according to claim 4, wherein,
Under the situation of first thermoplastic resin, along with the proportion rising/reduction by 0.01 of first thermoplastic resin, equilibrium humidity rising/decline RH 12%, and
Under the situation of second thermoplastic resin, along with the proportion rising/reduction by 0.01 of second thermoplastic resin, equilibrium humidity rising/decline RH 3%.
6. moisture absorbent molding, it comprises claim 1,2,3,4 and 5 each described moisture absorbent compositions.
7. the method for holding time of equilibrium humidity in the control moisture absorbent composition, it may further comprise the steps:
Apply the surface of the hygroscopic agent with equilibrium vapour pressure with fatty acid metal salts, said hygroscopic agent is by formula MgSO
4NH
2The magnesium sulfate that O representes is formed, in the formula, and 0≤n≤3; With
It is 1～40 μ m that hygroscopic agent is mediated the secondary particle particle diameter that has when making hygroscopic agent be distributed in the thermoplastic resin in the thermoplastic resin, and said thermoplastic resin is selected from the group that following material is formed: polyethylene, polypropylene, PET, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, PBT, ABS, polyamide, polystyrene, polyvinyl alcohol, Merlon, ethylene-methyl acrylate copolymer, polyacetals, ethylene-vinyl acetate copolymer, polyacrylate, PLA, polyimides, methyl methacrylate, cellulose acetate and celluloid; Thereby
Holding time of equilibrium humidity prolongs along with the increase of hygroscopic agent percent by weight content in thermoplastic resin.
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| EP2732866B1 (en) * | 2011-07-15 | 2016-10-19 | Tomita Pharmaceutical Co., Ltd. | Methof for producing magnesium sulfate-based desiccant |
| JP6089602B2 (en) * | 2012-11-02 | 2017-03-08 | 日立化成株式会社 | Prepreg storage method, laminate, and laminate package |
| US20140264167A1 (en) * | 2013-03-15 | 2014-09-18 | Multisorb Technologies, Inc. | Water vapor barrier composition |
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| JP5858311B1 (en) * | 2015-01-23 | 2016-02-10 | 富田製薬株式会社 | Hygroscopic inorganic filler-containing polyolefin composition and molded body using the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113457647A (en) * | 2021-07-29 | 2021-10-01 | 东南大学 | Cobalt-modified carbon-based fiber membrane and preparation method thereof |
| CN113457647B (en) * | 2021-07-29 | 2024-04-09 | 东南大学 | Cobalt modified carbon-based fiber membrane and preparation method thereof |
| CN115895241A (en) * | 2022-11-30 | 2023-04-04 | 惠州市保瑞新材料有限公司 | Packaging material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008026597A1 (en) | 2008-03-06 |
| US7473300B2 (en) | 2009-01-06 |
| EP2058372A1 (en) | 2009-05-13 |
| JP3979542B1 (en) | 2007-09-19 |
| EP2058372B1 (en) | 2020-01-15 |
| CN101360792A (en) | 2009-02-04 |
| EP2058372A4 (en) | 2010-09-15 |
| CN101360792B (en) | 2011-11-23 |
| CN102357331B (en) | 2014-06-11 |
| JP2008056784A (en) | 2008-03-13 |
| US20080058205A1 (en) | 2008-03-06 |
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